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Supported Acid Catalysts, Their Preparation And Use In Organic Compound Conversion - Patent 5294578

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Supported Acid Catalysts, Their Preparation And Use In Organic Compound Conversion - Patent 5294578 Powered By Docstoc
					


United States Patent: 5294578


































 
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	United States Patent 
	5,294,578



 Ho
,   et al.

 
March 15, 1994




 Supported acid catalysts, their preparation and use in organic compound
     conversion



Abstract

A novel method to prepare a solid acid catalyst through the reaction of a
     metal-alkyl halide species and the surface hydroxyl group of a solid
     support is disclosed. Lewis acidic metals, e.g., B, Al and Ga, etc., can
     then be anchored on the surface via the formation of an oxygen-metal bond.
     The solids containing these metals can be used as catalysts that will
     catalyze organic compound coversion reactions, e.g., Friedel-Crafts type
     reactions, olefin oligomerization, aromatic alkylation and acylation,
     alkane alkylation and isomerization reactions.


 
Inventors: 
 Ho; Suzzy C. (Plainsboro, NJ), Wu; margaret M. (Skillman, NJ) 
 Assignee:


Mobil Oil Corp.
 (Fairfax, 
VA)





Appl. No.:
                    
 07/996,385
  
Filed:
                      
  December 23, 1992





  
Current U.S. Class:
  502/62  ; 502/152; 502/154; 502/227; 502/231; 502/63; 502/64; 502/80
  
Current International Class: 
  B01J 37/00&nbsp(20060101); B01J 37/08&nbsp(20060101); B01J 37/02&nbsp(20060101); C07C 2/66&nbsp(20060101); C07C 2/00&nbsp(20060101); B01J 029/04&nbsp()
  
Field of Search: 
  
  














 502/150,151,224,263,414,171,231,355,62,63,64,80,152,154,227
  

References Cited  [Referenced By]
U.S. Patent Documents
 
 
 
3248343
April 1966
Kelly et al.

4719190
January 1988
Drago et al.

4740652
April 1988
Frame

5166410
November 1992
Fried



   
 Other References 

Inorganic Chemistry, vol. 29, No. 6, 1990, pp. 1186-1192.
.
Krzywicki et al., "Superacidity of Modified Gamma-Al.sub.2 O.sub.3 ", J. C. S. Faraday I, 1980, 76, 1311-1322..  
  Primary Examiner:  Garvin; Patrick P.


  Assistant Examiner:  Peebles; Brent M.


  Attorney, Agent or Firm: McKillop; Alexander J.
Santini; Dennis P.
Hobbes; Laurence P.



Claims  

It is claimed:

1.  A method of preparing a catalyst composition consisting essentially of halides of a single metal component anchored on an adsorbent solid by an oxygen-metal bond which comprises
contacting an adsorbent inorganic oxide support containing surface hydroxyl groups with organic metal halide, under conditions sufficient for said organic metal halide to react with at least a portion of said surface hydroxyl groups wherein said metal is
aluminum, and said adsorbent inorganic oxide support is selected from the group consisting of silica, silica-alumina, clay, crystalline porous silicates, silicoaluminophosphates, titania, vanadia, and rare earth oxides.


2.  The method of claim 1 wherein said surface hydroxyl groups are silanol, said organic metal halide has the formula RMXY wherein R is alkyl or aryl, M is aluminum, X is halogen and Y is selected from the group consisting of halogen, alkyl,
alkenyl, aryl, alkoxy, and amido moieties.


3.  The method of claim 1 wherein said inorganic oxide support is calcined at temperatures ranging from 100.degree.  to 900.degree.  C. prior to said contacting.


4.  The method of claim 1 wherein said inorganic oxide support is calcined at temperatures ranging from 300.degree.  C. to 600.degree.  C. for 1 to 8 hours, prior to said contacting.


5.  The method of claim 1 wherein said halides of a single metal component are present in the amount of 0.01 to 10 mmole/g of said catalyst composition.


6.  The method of claim 1 wherein said inorganic oxide support is silica.


7.  The method of claim 1 wherein said inorganic oxide support is a porous crystalline silicate selected from the group consisting of MCM-22 and MCM-41.


8.  The method of claim 2 wherein R is alkyl and Y is selected from the group consisting of halogen and alkyl.


9.  The method of claim 8 wherein X is Cl.


10.  The method of claim 2 wherein RMXY is selected from the group consisting of etAlCl.sub.2, Me.sub.2 AlCl, Et.sub.2 AlCl, Et.sub.2 AlCl/EtAlCl.sub.2, and Et.sub.2 AlOMe.


11.  The method of claim 2 wherein RMXY is EtAlCl.sub.2 and said adsorbent is silica.


12.  The method of claim 1 wherein said conditions comprise temperatures of -78.degree.  to 120.degree.  C., pressures of 10.sup.-6 to 10 atm, and reaction time of 0.01 to 10 hours.


13.  The method of claim 1 wherein said conditions comprise temperatures of 20.degree.  to 60.degree.  C., pressures of 0.1 to 1 atm, and reaction time of 0.5 to 2 hours.


14.  The catalyst composition prepared according to the method of claim 1.


15.  The catalyst composition prepared according to the method of claim 2.  Description  

BACKGROUND OF THE INVENTION


1.  Field of the Invention


This invention relates to supported acid catalysts, their method of preparation and use in hydrocarbon conversion reactions.  The catalyst composition contains metal halides on a solid inorganic oxide support.  The composition is prepared by
reacting an adsorbent solid support containing surface hydroxide groups with organic metal halide wherein said metal is a single element selected from one of Groups IIA, IIB, IIIA, IIIB, IVB, VB, and VIB, e.g., Al, under conditions sufficient for the
organic metal halide to react with at least a portion of the surface hydroxyl groups.


2.  Prior Art


Conventional Friedel-Crafts catalysts, e.g., AlCl.sub.3 and BF.sub.3, have been used extensively in many industrial processes as well as in the laboratory.  The major drawback of these systems is the need to dispose of large volumes of liquid and
gaseous effluents produced during subsequent quenching and product washing.  Replacing these processes by those based on heterogeneous catalysis has environmental and economic advantages, e.g., ease of separation, catalyst recycling and elimination of
quenching and washing steps.


The literature discloses efforts to anchor AlCl.sub.3 onto a solid support.  Alumina can be chlorided with AlCl.sub.3, HCl, or Cl.sub.2.  U.S.  Pat.  No. 3,248,343 to Kelly et al. teaches the treatment of surface hydroxyl-containing supports,
e.g., alumina or silica gel, with aluminum halide and thereafter treating with hydrogen halide.  Refluxing AlCl.sub.3 with solid supports, e.g., silica, in chlorinated solvent, e.g., CCl.sub.4, is an alternate way of anchoring Lewis acid onto a support
as disclosed in U.S.  Pat.  No. 4,719,190 to Drago et al and Getty et al., "Preparation, Characterization, and Catalytic Activity of a New Solid Acid Catalyst System," Inorganic Chemistry, Vol. 29, No. 6, 1990 1186-1192.  However, these methods suffer
from incomplete reaction between AlCl.sub.3, HCl or Cl.sub.2 and the support, resulting in a catalyst that either contains a low concentration of the acidic species or is not very stable due to the leachability of physisorbed or chemisorbed AlCl.sub.3
species from the solid support.  Krzywicki et al., "Superacidity of Modified Gamma-Al.sub.2 O.sub.3, " J.C.S.  Faraday I, 1980, 76 1311-1322, teach the treatment of alumina with a metal-alkyl species, e.g., CH.sub.3 AlCl.sub.2 vapors, to prepare a
superacid catalyst which can catalyze the transformation of saturated hydrocarbons.  U.S.  Pat.  No. 4,740,652 to Frame discloses an olefin oligomerization catalyst which comprises a porous support, e.g., silica, and plural metal components, an iron
group metal, e.g., Ni, and alkyl aluminum compound, e.g., diethylaluminum chloride and aluminum halide, e.g., aluminum trichloride.  Such catalysts are used in transition metal catalyzed chemistry.


BRIEF SUMMARY OF THE INVENTION


The present invention relates to a method of preparing a catalyst composition consisting essentially of halides of a single metal component anchored on an adsorbent solid by an oxygen-metal bond.  The method comprises contacting an adsorbent
inorganic oxide support containing surface hydroxyl groups with organic metal halide, under conditions sufficient for the organic metal halide to react with at least a portion of the surface hydroxyl groups.  The metal can be a single element selected
from one of Groups IIA, IIB, IIIA, IIIB, IVB, VB, and VIB, and the adsorbent inorganic oxide support is selected from the group consisting of silica, silica-alumina, clay, crystalline porous silicates, silicoaluminophosphates, titania, vanadia, and rare
earth oxides.  Reaction between the organic metal halide and the surface hydroxyl group can proceed readily at moderate conditions, e.g., room temperature and atmospheric pressure, eliminating the organic ligand and forming a metal-oxygen bond.  For
example, aluminum alkyl halide reacts with surface hydroxyl groups of a silanol-containing support as follows: ##STR1##


The catalyst compositions thus prepared comprise Lewis acidic catalysts, e.g., AlCl.sub.3, BF.sub.3, and GaCl.sub.3, anchored on the support surface by formation of an oxygen-metal bond.  The resulting solid catalysts containing these metals will
catalyze hydrocarbon conversion reactions such as Friedel-Crafts type reactions, olefin oligomerization, aromatic alkylation, alkane alkylation and isomerization reactions.


In another aspect, the invention relates to the preparation of a solid acid catalyst composition which consists essentially of halides of at least one major group element (non-transition elements) on an inorganic oxide adsorbent solid support
containing surface silanol groups.  Such major group metals include Lewis acidic metals such as Al, B, and Ga.  Such a composition is prepared by reacting an adsorbent solid support containing surface silanol groups with organic metal halide wherein said
metal is one or more major group elements, e.g., Lewis acidic metals (e.g., Al, B, and Ga), under conditions sufficient for the organic metal halide to react with at least a portion of the surface hydroxyl groups. 

DETAILED DESCRIPTION OF THE
INVENTION


The inorganic porous support materials useful in the present invention are typically inorganic oxides of silica, silica-alumina, silica-thoria, silica-zirconia, clays, crystalline silicates, e.g., zeolites, and silicoaluminophosphates (SAPOs) and
comparable oxides which are porous, and have surface hydroxyl groups, viz., silanol groups.  Other suitable inorganic porous support materials include titania, zirconia, alumina, vanadia, and rare-earth oxides which have surface hydroxyl groups.


Preferred silica support materials are amorphous silica, silica gels or xerogels with high porosity, preferably having pores of at least 10 Angstroms, more preferably at least 20 Angstroms, e.g., 20 to 460 Angstroms or 60 to 250 Angstroms. 
Suitable particle sizes for such silica supports range from 1 to 600 mesh, preferably 30 to 400 mesh, e.g., 30 to 60 or 90 to 300 mesh size.  The solid support materials can be calcined, preferably under an inert gas, e.g., nitrogen, at a suitable
temperature for a sufficient time to remove physically-bound water and/or to partially remove chemically-bound water.  Such temperatures can range from about 100.degree.  to 900.degree.  C., preferably 300.degree.  to 600.degree.  C., and contacting
times can range from 0.1 to 24 hours, preferably 1 to 8 hours.  The extent of loading of the halides of a single metal component on the hydroxyl-containing support can be increased by moderating the calcination carried out upon the support prior to
contact with the organic metal halide, e.g, reducing calcination temperatures from about 600.degree.  C. to 300.degree.  C. This is especially effective with silica gel supports.  Generally, after treatment with organic metal halide, the metal halides
are present in the amount of 0.01 to 10 mmole/g of the catalyst composition.


Naturally occurring clays which can be used as supports herein include the montmorillonite and kaolin families which include the subbentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays, or others in which the
main mineral constituent is halloysite, kaolinite, dickite, nacrite or anauxite.  Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification.


Zeolitic materials, both natural and synthetic, have been demonstrated in the past to have catalytic properties for various types of hydrocarbon conversion.  Certain zeolitic materials are ordered, porous crystalline aluminosilicates having a
definite crystalline structure as determined by X-ray diffraction, within which there are a large number of smaller cavities which may be interconnected by a number of still smaller channels or pores.  These cavities and pores are uniform in size within
a specific zeolitic material.  Since the dimensions of these pores are such as to accept for adsorption molecules of certain dimensions while rejecting those of larger dimensions, these materials have come to be known as "molecular sieves" and are
utilized in a variety of ways to take advantage of these properties.


Such molecular sieves, both natural and synthetic, include a wide variety of positive ion-containing crystalline aluminosilicates.  These aluminosilicates can be described as rigid three-dimensional frameworks of SiO.sub.4 and AlO.sub.4 in which
the tetrahedra are cross-linked by the sharing of oxygen atoms whereby the ratio of the total aluminum and silicon atoms to oxygen atoms is 1:2.  The electrovalence of the tetrahedra containing aluminum is balanced by the inclusion in the crystal of a
cation, for example an alkali metal or an alkaline earth metal cation.  This can be expressed wherein the ratio of aluminum to the number of various cations, such as Ca/2, Sr/2, Na, K or Li, is equal to unity.  One type of cation may be exchanged either
entirely or partially with another type of cation utilizing ion exchange techniques in a conventional manner.  By means of such cation exchange, it has been possible to vary the properties of a given aluminosilicate by suitable selection of the cation. 
The spaces between the tetrahedra are occupied by molecules of water prior to dehydration.


Prior art techniques have resulted in the formation of a great variety of synthetic zeolites.  The zeolites have come to be designated by letter or other convenient symbols, as illustrated by zeolite A (U.S.  Pat.  No. 2,882,243), zeolite X (U.S. Pat.  No. 2,882,244), zeolite Y (U.S.  Pat.  No. 3,130,007), zeolite ZK-5 (U.S.  Pat.  No. 3,247,195), zeolite ZK-4 (U.S.  Pat.  No. 3,314,752), zeolite ZSM-5 (U.S.  Pat.  No. 3,702,886), zeolite ZSM-11 (U.S.  Pat.  No. 3,709,979), zeolite ZSM-12 (U.S. 
Pat.  No. 3,832,449), zeolite ZSM-20 (U.S.  Pat.  No. 3,972,983), zeolite ZSM-35 (U.S.  Pat.  No. 4,016,245), zeolite ZSM-38 (U.S.  Pat.  No. 4,046,859), zeolite ZSM-23 (U.S.  Pat.  No. 4,076,842) and MCM-22 (U.S.  Pat.  No. 4,954,325) merely to name a
few.


Silicoaluminophosphates of various structures are taught in U.S.  Pat.  No. 4,440,871 include SAPO-5, SAPO-11, SAPO-16, SAPO-17, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-37, SAPO-40, SAPO-41, SAPO-42, and SAPO-44.  Other teachings of
silicoaluminophosphates and their synthesis include U.S.  Pat.  No. 4,673,559 (two-phase synthesis method); 4,623,527 (MCM-10); 4,639,358 (MCM-1); 4,647,442 (MCM-2); 4,664,897 (MCM-4); 4,639,357 (MCM-5); 4,632,811 (MCM-3); and 4,880,611 (MCM-9).


Mesoporous siliceous materials are recent developments in catalyst technology having novel pore geometry which are suitable as molecular sieves having openings of at least 8 Angstroms which are used as components of the layered catalyst of the
present invention.  Such materials can be described as inorganic, porous non-layered crystalline phase material exhibiting, after calcination, an X-ray diffraction pattern with at least one peak at a d-spacing greater than about 18 Angstrom Units and
having a benzene adsorption capacity of greater than 15 grams benzene per 100 grams of said calcined material at 50 torr and 25.degree.  C. Such materials can further be characterized by substantially uniform hexagonal honeycomb microstructure, with
uniform pores having a cell diameter greater than 13 Angstrom units, say, 15 Angstrom Units (preferably in the mesoporous range of about 20-100A).  Most prominent among these ultra-large pore size materials is a class of materials known as M41S which are
described further in U.S.  Pat.  No. 5,102,643, including a metallosilicate called MCM-41, which is usually synthesized with Bronsted acid active sites by incorporating a tetrahedrally coordinated trivalent element, such as Al, Ga, B, or Fe, within the
silicate framework.  Aluminosilicate materials of this type are thermally and chemically stable, properties favored for acid catalysis; however, the advantages of mesoporous structures may be utilized by employing highly siliceous materials or
crystalline metallosilicate having one or more tetrahedral species having varying degrees of acidity.  In addition to the preferred aluminosilicates, the gallosilicate, ferrosilicate and borosilicate materials may be employed.  Although matrices may be
formed with the germanium analog of silicon, these are expensive and generally no better than the metallosilicates.


MCM-41 crystalline structure is readily recognized by its spectrographic characteristics, such as electron micrograph, X-ray diffraction pattern, absorption properties, etc., as described in U.S.  Pat.  No. 5,098,684.


All of the above patents are incorporated herein by reference.


The organic metal halide employed in the present invention can comprise one or more metal elements selected from Groups IIA, IIB, IIIA, IIIB, IVB, VB, and VIB of the Periodic Table, under conditions sufficient for the organic metal halide to
react with at least a portion of the surface hydroxyl groups.  Suitable organic metal halides include those represented by the formula RMXY wherein R is alkyl, alkenyl, or aryl, M is an element selected from Groups IIA, IIB, IIIA, IIIB, IVB, VB, and VIB
of the Periodic Table, X is halogen and Y is selected from the group consisting of halogen, alkyl, alkenyl, aryl, alkoxy, and amido moities.  In one embodiment, R is alkyl, M is a Group IIIA element, e.g., Al, B, or Ga, and Y is selected from the group
consisting of halogen, e.g., Cl or Br, and alkyl.  A particularly preferred organic metal halide is one wherein RMXY is selected from the group consisting of EtAlCl.sub.2, Me.sub.2 AlCl, Et.sub.2 AlCl, Et.sub.2 AlCl/EtAlCl.sub.2, and Et.sub.2 AlOMe, with
EtAlCl.sub.2 particularly preferred.


Generally, the support is combined with a suitable solvent in amounts sufficient to form a slurry.  The slurry is then combined with the organic metal halide which can also be combined with a suitable solvent in order to facilitate handling and
mixing.  Such solvents are preferably inert to reaction with the support and organic metal halide.  Examples of suitable solvents include alkanes which are liquid under standard conditions such as C.sub.4 to C.sub.16 alkanes, e.g., n-pentane, n-hexane,
or n-heptane.


The conditions used to prepare the catalysts of the present invention are those which allow the organic metal halide to react with at least a portion of the surface hydroxyl groups on the adsorbent solid support.  Suitable conditions for
contacting the support with organic metal halide comprise temperatures of -78.degree.  to 120.degree.  C., pressures of 10.sup.-6 atm to 10 atm, and reaction time of 0.01 to 10 hours.  Preferred conditions include temperatures of 20.degree.  to
60.degree.  C., pressures of 10.sup.-1 to 1 atm, and reaction time of 0.5 to 2 hours.  It is preferred that the catalysts of the present invention be prepared under an inert atmosphere, e.g., nitrogen or helium, in order to prevent unwanted hydrolysis of
the organic metal halides.  Such conditions can be obtained using conventional Schlenk line techniques.


Following the reaction, the catalyst may be separated from the reaction mixture according to any conventional procedure for removing solids from the liquid solvent medium, e.g., decantation or filtration.  The catalyst is ready for use after the
drying step as described below.  In another method of preparation, the resulting solid can be washed with a suitable liquid, e.g. inert organics, e.g., anhydrous C.sub.4 to C.sub.6 alkanes, e.g., n-hexane.  Such washing is preferably carried out a
sufficient number of times to substantially remove excess organic metal halides.  The washed catalyst is then dried, preferably under vacuum, at temperatures ranging from 0.degree.  to 120.degree.  C., preferably 20.degree.  to 60.degree.  C. The dried
catalyst is then stored under inert atmosphere, e.g., in a nitrogen filled box.


The amount of metal halides or organo-metal halides deposited onto the solid can range from 0.01 mmole to 10 mmoles of metal halides or organometal halides per g of catalyst.  Generally, the lower calcination temperature for the solid, the more
organometal halide one can deposit onto the solid.


The catalyst thus prepared is suited to use in the catalytic conversion of organic, e.g., hydrocarbon feeds.  In general, catalytic conversion conditions over the present catalyst include a temperature of from about -100.degree.  C. to about
760.degree.  C., a pressure of from about 0.1 atmosphere (bar) to about 200 atmospheres (bar), a weight hourly space velocity of from 0.08 to 2000 hr.sup.-1 and a hydrogen/organic, e.g., hydrocarbon, compound ratio of from 0 to 100.


Non-limiting examples of such conversion processes include: cracking hydrocarbons with reaction conditions including a temperature of 300.degree.  to 700.degree.  C., a pressure of 0.1 to 30 atmospheres (bar) and a weight hourly space velocity of
from 0.1 to 20 hr.sup.-1 ; dehydrogenating hydrocarbon compounds with reaction conditions including a temperature of 300.degree.  to 700.degree.  C., a pressure of 0.1 to 10 atmospheres (bar) and a weight hourly space velocity of from 0.1 to 20 hr.sup.-1
; converting paraffins to aromatics with reaction conditions including a temperature of 100.degree.  to 700.degree.  C., a pressure of 0.1 to 60 atmospheres (bar) and a weight hourly space velocity of from 0.5 to 400 hr.sup.-1 and a hydrogen/hydrocarbon
ratio of from 0 to 20; converting olefins to aromatics, e.g., benzene, toluene and xylenes, with reaction conditions including a temperature of 100.degree.  to 700.degree.  C., a pressure of 0.1 to 60 atmospheres (bar) and a weight hourly space velocity
of from 0.5 to 400 hr.sup.-1 and a hydrogen/hydrocarbon ratio of from 0 to 20; converting alcohols, e.g., methanol, or ethers, e.g., dimethylether, or mixtures thereof, to hydrocarbons including aromatics with reaction conditions including a temperature
of 275.degree.  to 600.degree.  C., a pressure of 0.5 to 50 atmospheres (bar) and a weight hourly space velocity of from 0.5 to 100 hr.sup.-1 ; isomerizing xylene feedstock components with reaction conditions including a temperature of 230.degree.  to
510.degree.  C., a pressure of 3 to 35 atmospheres (bar), a weight hourly space velocity of from 0.1 to 200 hr.sup.-1, and a hydrogen/hydrocarbon ratio of from 0 to 100; disproportionating toluene with reaction conditions including a temperature of
200.degree.  to 760.degree.  C., a pressure of atmospheric to 60 atmospheres (bar) and a weight hourly space velocity of from 0.08 to 20 hr.sup.-1.


The catalysts of the present invention are particularly useful in processes which rely on a cationic mechanism, e.g., acidic catalysis reactions.  All these reactions can be carried out in a fixed-bed, continuous flow reactor or in a slurry,
batch-type operation or continuous stirred tank reactor (CSTR) type operation.  Such reactions include olefin oligomerization or polymerization reactions with reaction conditions including a temperature of -100.degree.  to 300.degree.  C., preferably
-50.degree.  to 200.degree.  C., a pressure of 10.sup.-6 to 60 atmospheres (bar), preferably 0.1 to 10 atmospheres (bar) and a weight hourly space velocity of from 0.1 to 400, preferably 0.1 to 20; Friedel-Crafts alkylation reactions with olefins, alkyl
halides or benzyl halides, with reaction conditions including a temperature of -100.degree.  to 300.degree.  C., preferably -50.degree.  to 200.degree.  C., a pressure of 0.1 to 60 atmospheres (bar), preferably 0.1 to 10 atmospheres (bar) and a weight
hourly space velocity of from 0 1 to 400, preferably 0.1 to 20; and alkane isomerization reactions with reaction conditions including a temperature of 0.degree.  to 400.degree.  C., preferably 100.degree.  to 300.degree.  C., a pressure of 0.1 to 60
atmospheres (bar), preferably 0.1 to 20 atmospheres (bar) and a weight hourly space velocity of from 0.1 to 400, preferably 0.1 to 20.


In order to more fully illustrate the nature of the invention and the manner of practicing same, the following examples are presented.  It will be understood that the examples are illustrative only and that various modifications may be made in
the specified parameters without departing from the scope of the invention.


EXAMPLE 1


In a 100 mL Schlenk flask was placed 10 g of 20A silica gel (calcined at 600.degree.  C. under nitrogen for 15 hours and stored under nitrogen atmosphere) and 40 mL of anhydrous hexane.  5 g of 25 wt % solution of EtAlCl.sub.2 in hexane was added
to the slurry via syringe.  During the addition-step a stoichiometric amount of ethane evolution was observed.  The mixture was stirred at room temperature for one hour.  The supernatant was removed and the solids were washed with 20 mL of anhydrous
hexane three times.  The solids were dried under vacuum at room temperature or 50.degree.  C. for one hour.


EXAMPLES 2-12


The method in Example 1 was used with different silica and reagents as indicated in Table 1.


 TABLE 1  __________________________________________________________________________ Catalyst Preparation  CALCINATION Al:SUPPORT  EXAMPLE  SUPPORT  TEMP* REAGENT  (mmol:g) 
__________________________________________________________________________ 1 20A silica  600.degree. C.  EtAlCl.sub.2  <<1.0:1**  2 40A silica  600.degree. C.  EtAlCl.sub.2  1.0:1  3 60A silica  600.degree. C.  EtAlCl.sub.2  1.0:1  4 150A silica 
600.degree. C.  EtAlCl.sub.2  1.0:1  5 60A silica  300.degree. C.  EtAlCl.sub.2  1.0:1  6 60A silica  300.degree. C.  EtAlCl.sub.2  2.0:1  7 60A silica  600.degree. C.  EtAlCl.sub.2  2.0:1  8 60A silica  600.degree. C.  Me.sub.2 AlCl  1.0:1  9 60A silica 600.degree. C.  Et.sub.2 AlCl  1.0:1  10 60A silica  600.degree. C.  Et.sub.2 AlCl/  EtAlCl.sub.2  1.0:1  11 60A silica  600.degree. C.  Et.sub.2 AlOMe  1.0:1  12 50A MCM-41  538.degree. C.  EtAlCl.sub.2  1.0:1  8 gamma Al.sub.2 O.sub.3  600.degree. C. 
EtAlCl.sub.2  1.0:1  __________________________________________________________________________ *By titration, SiO2 calcined at 300.degree. C. contains 3.0 mmol of  Si--OH/g of SiO.sub.2  By titration, SiO2 calcined at 600.degree. C. contains 2.1 mmol of Si--OH/g of SiO.sub.2  **Reaction between Si--OH and EtAlCl.sub.2 was minimal as indicated by th  removal of EtAlCl.sub.2 during subsequent hexane wash.


EXAMPLES 14-24


The activities of the catalysts shown in Table 1 were tested for aromatic alkylation with toluene and 1-hexane and the results are shown in Table 2.


a) The activities depend on pore size of the silica.  Extremely low hexene conversion was observed for catalyst prepared from the 20A silica.  This is the result of lower amount of Al deposited (see Table 1) on the SiO.sub.2 as well as the small
pore size.  The catalyst prepared from the 40A silica is less active achieving only 15% hexene conversion in one hour compared to 99% conversions of similar catalysts prepared from 60A and 150A silica;


b) As expected, the catalyst with two chlorine ligands on the aluminum is more active than those containing at least one alkyl or alkoxy ligand.  Since alkyl and alkoxy groups are electron donating, the aluminum center with those ligands are less
Lewis acidic than those with two chlorine ligands;


c) Catalysts prepared from supports (Examples 3 and 9) calcined at two difference temperatures do not show significant difference in the toluene-hexene alkylation reaction; and


d) Catalysts with different aluminum loading cannot be differentiated by the toluene-hexene reaction at room temperature.


 TABLE 2  __________________________________________________________________________ Toluene Alkylation with 1-Hexene  (20 mL of Toluene and 10 mL of 1-Hexene  over 0.5 g of Catalyst at Room Temperature)  PRODUCT DISTRIBUTION  REACTION  %
1-HEXENE  (ALKYLATED)  EXAMPLE  CATALYST  TIME, h  CONVERSION  MONO-  DI-  TRI-  __________________________________________________________________________ 14 Ex. 1 20 0.1 -- -- --  15 Ex. 2 1 14.8 59.1 21.4  19.5  16 Ex. 3 1 99.0 64.2 24.2  11.6  17 Ex.
4 1 99.0 64.9 27.1  8.0  18 Ex. 5 1 94.5 71.8 22.1  6.1  19 Ex. 6 1 98.8 73.1 22.5  4.4  20 Ex. 7 1 98.4 59.3 25.2  15.5  21 Ex. 8 48 97.1 63.1 22.8  9.2  22 Ex. 9 90 18.9 75.9 15.0  7.5  23 Ex. 10  99 98.1 59.3 23.5  17.2  24 Ex. 11  49 0.2 67.9 22.8 
9.2  __________________________________________________________________________


EXAMPLES 25-34


The catalyst prepared according to Example 3 was used for various Friedel-Crafts aromatic alkylation reactions shown in Table 3.


 TABLE 3  __________________________________________________________________________ Friedel-Crafts Aromatic Alkylation  REACTANT CONVERSION  AROMATIC ALKYLATING  RATIO (mole)  ALKYLATING  Ex.  COMPOUND (1)  AGENT (2)  1:2:CATALYST  CONDITION 
AGENT  __________________________________________________________________________ 25 Benzene 1-Decene 222:111:1  <34.degree. C.,  2 h  99%  26 Diphenylether  1-Dodecene  222:111:1  100.degree. C.,  3.5 h  80%  27 Naphthalene  1-Dodecene  222:111:2 
48.degree. C.,  19 h  98%  28 Phenol 1-Dodecene  111:55:1 100.degree. C.,  19 h  1.5%  29 Benzene 2-Chlorobutane  555:28:1 50.degree. C.,  1 h  99%  30 Benzene Dibromomethane  555:28:1 50.degree. C.,  2.5 h  45%  31 Benzene Dichlorotoluene  555:28:1
50.degree. C.,  17 h  21%  32 Chlorobenzene  Dichlorotoluene  555:28:1 50.degree. C.,  1 h  41%  33 Benzene Benzyl chloride  555:55:1 50.degree. C.,  2.5 h  56%  34 Fluorobenzene  Benzyl chloride  555:55:1 50.degree. C.,  19 h  50% 
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DOCUMENT INFO
Description: 1. Field of the InventionThis invention relates to supported acid catalysts, their method of preparation and use in hydrocarbon conversion reactions. The catalyst composition contains metal halides on a solid inorganic oxide support. The composition is prepared byreacting an adsorbent solid support containing surface hydroxide groups with organic metal halide wherein said metal is a single element selected from one of Groups IIA, IIB, IIIA, IIIB, IVB, VB, and VIB, e.g., Al, under conditions sufficient for theorganic metal halide to react with at least a portion of the surface hydroxyl groups.2. Prior ArtConventional Friedel-Crafts catalysts, e.g., AlCl.sub.3 and BF.sub.3, have been used extensively in many industrial processes as well as in the laboratory. The major drawback of these systems is the need to dispose of large volumes of liquid andgaseous effluents produced during subsequent quenching and product washing. Replacing these processes by those based on heterogeneous catalysis has environmental and economic advantages, e.g., ease of separation, catalyst recycling and elimination ofquenching and washing steps.The literature discloses efforts to anchor AlCl.sub.3 onto a solid support. Alumina can be chlorided with AlCl.sub.3, HCl, or Cl.sub.2. U.S. Pat. No. 3,248,343 to Kelly et al. teaches the treatment of surface hydroxyl-containing supports,e.g., alumina or silica gel, with aluminum halide and thereafter treating with hydrogen halide. Refluxing AlCl.sub.3 with solid supports, e.g., silica, in chlorinated solvent, e.g., CCl.sub.4, is an alternate way of anchoring Lewis acid onto a supportas disclosed in U.S. Pat. No. 4,719,190 to Drago et al and Getty et al., "Preparation, Characterization, and Catalytic Activity of a New Solid Acid Catalyst System," Inorganic Chemistry, Vol. 29, No. 6, 1990 1186-1192. However, these methods sufferfrom incomplete reaction between AlCl.sub.3, HCl or Cl.sub.2 and the support, resulting in a catalyst that either c